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United States Patent |
5,773,666
|
Omatsu
,   et al.
|
June 30, 1998
|
Hydroformylation process
Abstract
Described is a process for hydroformylation of an olefinic compound, which
comprises, carrying out the reaction in the presence of:
a) a rhodium compound,
b) a tertiary organic phosphorus compound represented by the following
formula (1):
P(X.sub.1)(X.sub.2)(X.sub.3 --SO.sub.3 M) (1)
wherein X.sub.1 and X.sub.2 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms and X.sub.3 represents a
divalent hydrocarbon group having 1-15 carbon atoms and M represents an
alkali metal, and
c) a polar organic compound; separating the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound from the resulting reaction mixture by extraction with
water; subjecting the extracted water layer to removal of water and
addition of at least one acidic substance selected from sulfonic acids to
prepare a concentrate containing the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound; and recycling the resulting concentrate to a reactor for
reuse.
Inventors:
|
Omatsu; Toshihiro (Hasaki-machi, JP);
Tokuyasu; Jin (Kamisu-machi, JP);
Muranaka; Masahiro (Kamisu-machi, JP);
Onishi; Takashi (Hasaki-machi, JP)
|
Assignee:
|
Kuraray Co., Ltd. (Kurashiki, JP)
|
Appl. No.:
|
836880 |
Filed:
|
May 27, 1997 |
PCT Filed:
|
September 26, 1996
|
PCT NO:
|
PCT/JP96/02771
|
371 Date:
|
May 27, 1997
|
102(e) Date:
|
May 27, 1997
|
PCT PUB.NO.:
|
WO97/11931 |
PCT PUB. Date:
|
April 3, 1997 |
Foreign Application Priority Data
Current U.S. Class: |
568/454; 568/451 |
Intern'l Class: |
C07C 045/50 |
Field of Search: |
568/454,451
|
References Cited
U.S. Patent Documents
5180854 | Jan., 1993 | Abatjoglou et al. | 568/454.
|
Foreign Patent Documents |
52-105590 A | Sep., 1977 | JP.
| |
58-208243 A | Dec., 1983 | JP.
| |
63-190844 A | Aug., 1988 | JP.
| |
Primary Examiner: Geist; Gary
Assistant Examiner: Padmanabhan; Sreeni
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt, P.C.
Claims
We claim:
1. A process for the hydroformylation of an olefinic compound, which
comprises, upon the reaction of the olefinic compound with hydrogen and
carbon monoxide, carrying out the reaction in the presence of:
a) a rhodium compound
b) a tertiary organic phosphorous compound represented by the following
formula (1):
P(X.sub.1)(X.sub.2)(X.sub.3 --SO.sub.3 M) (1)
wherein X.sub.1 and X.sub.2 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms, X.sub.3 represents a divalent
hydrocarbon group having 1-15 carbon atoms and M represents an alkali
metal, and
c) a polar organic compound; separating the rhodium compound, the tertiary
organic phosphorous compound represented by the formula (1) and the polar
organic compound from the resulting reaction mixture by extraction with
water; subjecting the extracted water layer to removal of water and
addition of at least one acidic substance selected from sulfonic acids in
an amount to adjust the pH of the extracted water layer to at least about
neutral to prepare a concentrate containing the rhodium compound, the
tertiary organic phosphorous compound represented by the formula (1) and
the polar organic compound; and recycling the resulting concentrate to a
reactor for reuse.
2. The hydroformylation process of an olefinic compound according to claim
1, wherein the olefinic compound is an olefinic compound having a formyl
group or an olefinic compound which has at least two ethylenic double
bonds to which a formyl group is introduced by the hydroformylation
reaction.
3. The hydroformylation process of an olefinic compound according to claim
1, wherein the polar organic compound is one or more than one compounds
selected from the group consisting of dimethyl sulfoxide, sulfolane,
ethylene carbonate, N-methylpyrrolidone, dimethylformamide, acetonitrile,
ethylene glycol, butanediol, polyalkylene glycols, polyalkylene glycol
monomethyl ethers and polyalkylene glycol dimethyl ethers.
4. The hydroformylation process of an olefinic compound according to claim
1, wherein the polar organic compound is a polyethylene glycol having a
number average molecular weight of not lower than 300 but not higher than
600 and/or polyethylene glycol dimethyl ether having a number average
molecular weight of not lower than 300 but not higher than 600.
5. The hydroformylation process of an olefinic compound according to claim
1, wherein the acidic substance is a phosphorus-containing sulfonic acid
represented by the following formula (2):
P(X.sub.4) (X.sub.5) (X.sub.6 --SO.sub.3 H) (2)
wherein X.sub.4 and X.sub.5 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms and X.sub.6 represents a
divalent hydrocarbon group having 1-15 carbon atoms.
6. A process for the preparation of a hydroformylated product of an
olefinic compound, which comprises, upon the reaction of the olefinic
compound with hydrogen and carbon monoxide, carrying out the reaction in
the presence of:
a) a rhodium compound
b) a tertiary organic phosphorous compound represented by the following
formula (1):
P(X.sub.1)(X.sub.2)(X.sub.3 --SO.sub.3 M) (1)
wherein X.sub.1 and X.sub.2 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms, X.sub.3 represents a divalent
hydrocarbon group having 1-15 carbon atoms and M represents an alkali
metal, and
c) a polar organic compound; separating the rhodium compound, the tertiary
organic phosphorous compound represented by the formula (1) and the polar
organic compound from the resulting reaction mixture by extraction with
water; subjecting the extracted water layer to removal of water and
addition of at least one acidic substance selected from sulfonic acids in
an amount to adjust the pH of the extracted water layer to at least about
neutral to prepare a concentrate containing the rhodium compound, the
tertiary organic phosphorous compound represented by the formula (1) and
the polar organic compound; and recycling the resulting concentrate to a
reactor for reuse.
Description
This is a 371 of PCT/JP96/02771, filed Sep. 26, 1995.
TECHNICAL FIELD
This invention relates to a process for the hydroformylation of an olefinic
compound. A hydroformylated product obtained by the present invention is
useful as a starting material for fine chemicals such as pharmaceuticals
and agricultural chemicals, alcohols for a plasticizer, or starting
materials such as diol, dicarboxylic acid, and diamine for the synthesis
of a polymer compound.
BACKGROUND ART
A process for preparing an aldehyde by the reaction of an olefinic compound
with hydrogen and carbon monoxide using a rhodium compound as a catalyst
is called hydroformylation reaction or oxo reaction and it is an
industrially useful synthetic process. The rhodium compound is, however,
markedly expensive. So, in order to carry out the hydroformylation
reaction in an industrially advantageous manner, a technique of recycling
the rhodium compound while maintaining its catalytic activity is required.
As a method for separating the reaction mixture into a rhodium catalyst and
a product in the hydroformylation reaction, there is a method using
distillation. Except the case where an aldehyde having a comparatively low
boiling point is produced, the above method using distillation can hardly
be regarded as advantageous from the viewpoint of the industrial practice,
because the rhodium catalyst is deteriorated by the heat at the time of
its separation by distillation. Particularly in the case where an aldehyde
to be produced has a high boiling point, the condensation of the product
tends to occur under the distillation conditions to form easily by-product
of a higher-boiling point condensed material. Such a higher-boiling point
condensed material is concentrated in a residual liquid in a still by
distillation and is accumulated gradually with the recycling of the
catalyst. This increases the viscosity of the residual liquid in the
still, so that, even if the catalytic activity of the catalyst is
maintained, the operability of the reaction is lost with the proceeding of
the production of the aldehyde, which actually prevents the recycling of
the catalyst. Furthermore, owing to heat, cross-linking reaction of this
higher-boiling point condensed material happens to occur, which solidifies
the residual liquid in the still and makes it impossible to carry out
recycling of the catalyst.
Owing to such a problem in the operability, it is inevitable to renew the
catalyst in a short time in the case of separating the rhodium catalyst
from the product by distillation, except the case where an aldehyde having
a relatively low boiling point is produced.
As a process for avoiding the above-described problem involved by the
separation of the catalyst from the product by distillation, Japanese
Patent Application Laid-Open No. SHO 58-157739 provides a process in
which, using a water-soluble rhodium catalyst, a hydroformylation reaction
is effected in the aqueous solvent and then the product is separated by
extraction using an extractant such as a hydrocarbon. In addition, U.S.
Pat. No. 5,180,854 discloses a process in which a hydroformylation
reaction is effected, with the water-soluble rhodium catalyst dissolved in
a reaction mixture using a solubilizing agent such as N-methylpyrrolidone,
and then the catalyst is separated by extraction using water as an
extractant.
The process disclosed in Japanese Patent Application Laid-Open No. SHO
58-157739 for the separation of the product by extraction is excellent in
that (1) the catalyst is free from the heat and deactivation and (2)
accumulation of the high-boiling point condensed material is avoided. But,
the process is not advantageous for the industrial application, because it
requires a large amount of a solvent and therefore a large-scaled reaction
apparatus, which lowers a volumetric efficiency of the reaction, and
moreover a great amount of energy upon the recovery of the extractant from
the extract.
On the other hand, the process disclosed in U.S. Pat. No. 5,180,854 for the
extraction of the catalyst is excellent in that i) the catalyst is free
from thermal deterioration, ii) accumulation of a high-boiling point
condensed material is avoided and iii) a high volumetric efficiency is
achieved.
The present inventors carried out the hydroformylation reaction of an
olefinic compound in accordance with the process disclosed in the above
U.S. patent in view of the above advantages i)-iii). It has been
recognized that the process is accompanied with the following problems.
Described specifically, while recycling of a catalyst is repeated,
selectivity to the byproduct which has a higher boiling point than the
target aldehyde increases with the proceeding of the production of the
aldehyde. This means that the selectivity to the target aldehyde decreases
with the proceeding of the production of the aldehyde. Such a byproduct
has an influence of the reduction of the recovery ratio of the catalyst or
extends the time necessary for the separation of the water layer
containing the catalyst. In addition, together with the lowering in the
selectivity to the target aldehyde, the lowering in the catalytic activity
has also been recognized.
Such problems appear notably in the case where a compound having at least
two aldehyde groups is obtained by carrying out hydroformylation reaction
of an olefinic compound having a formyl group, such as 7-octen-1-al, or of
an olefinic compound having at least two ethylenic double bonds to which a
formyl group is introduced by the hydroformylation reaction, such as
1,7-octadiene. For example, upon hydroformylation of 7-octen-1-al, the
selectivity to the high-boiling point condensed material which is a
byproduct finally becomes 10% or higher based on 7-octen-1-al.
In this way, even in the process described in U.S. Pat. No. 5,180,854,
there exist some problems to be solved in order to carry out the
hydroformylation reaction of an olefinic compound industrially
advantageously.
So, an object of the present invention is therefore to provide an
industrially advantageous process for the production of an aldehyde by the
hydroformylation of an olefinic compound using a rhodium catalyst, by
overcoming the problems such as thermal deterioration of the catalyst,
limitation in the recycling of the catalyst owing to the accumulation of a
high-boiling point condensed material, lowering in the volumetric
efficiency of the reaction caused by the use of a large volume of a
solvent, an increase in the selectivity to the high-boiling point
byproduct with the proceeding of the production of the aldehyde and the
lowering in the catalytic activity.
DISCLOSURE OF THE INVENTION
The present inventors have conducted an extensive research with a view to
overcome the above-described problems. As a result, the present inventors
have completed the present invention based on the finding that the
increase in the selectivity to the high-boiling point byproduct with the
proceeding of the production of an aldehyde and lowering in the catalytic
activity can be prevented by adding an acidic substance to a catalytic
component which has been separated from the hydroformylated product of an
olefinic compound by the extraction using water as an extractant and
recycling the resulting mixture for the hydroformylation reaction of the
olefinic compound.
In one aspect of the present invention, there is provided a process for the
hydroformylation of an olefinic compound, which comprises, upon the
reaction of an olefinic compound with hydrogen and carbon monoxide,
carrying out the reaction in the presence of:
a) a rhodium compound,
b) a tertiary organic phosphorus compound represented by the following
formula (1):
P(X.sub.1)(X.sub.2)(X.sub.3 --SO.sub.3 M) (1)
wherein X.sub.1 and X.sub.2 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms, X.sub.3 represents a divalent
hydrocarbon group having 1-15 carbon atoms and M represents an alkali
metal, and
c) a polar organic compound; separating the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound from the resulting reaction mixture by extraction with
water; subjecting the extracted water layer to removal of water and
addition of at least one acidic substance selected from sulfonic acids to
prepare a concentrate containing the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound; and recycling the resulting concentrate to a reactor for
reuse.
In another aspect of the present invention, there is also provided a
process for the preparation of a hydroformylated product of an olefinic
compound, which comprises, upon the reaction of an olefinic compound with
hydrogen and carbon monoxide, carrying out the reaction in the presence
of:
a) a rhodium compound,
b) a tertiary organic phosphorus compound represented by the above formula
(1), and
c) a polar organic compound; separating the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound from the resulting reaction mixture by extraction with
water; subjecting the extracted water layer to removal of water and
addition of at least one acidic substance selected from sulfonic acids to
prepare a concentrate containing the rhodium compound, the tertiary
organic phosphorus compound represented by the formula (1) and the polar
organic compound; and recycling the resulting concentrate to a reactor for
reuse.
BEST MODE FOR WORKING THE INVENTION
The present invention will be described in detail.
In the hydroformylation process of the present invention, an olefinic
compound to be hydroformylated is a compound which has an ethylenic
carbon-carbon double bond and permits the formation of a corresponding
aldehyde by the reaction with hydrogen and carbon monoxide. Such an
olefinic compound can contain a substituent which does not inhibit the
hydroformylation reaction. Examples of such a substituent include formyl
group; hydroxyl group; alkoxy groups such as methoxy and ethoxy;
alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and
t-butoxycarbonyl; cyano group; and halogen atoms such as chlorine and
bromine.
Specific examples of the olefinic compound include unsaturated hydrocarbons
such as 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, cyclohexene,
styrene, 1,5-hexadiene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene
and cyclooctadiene; unsaturated aldehydes such as 7-octen-1-al;
unsaturated alcohols such as 7-octen-1-ol and 2,7-octadien-1-ol;
acrylonitrile, vinyl acetate, vinyl chloride and methyl methacrylate.
The hydroformylation process of the present invention is particularly
useful in the case where a compound having at least two aldehyde groups is
prepared using as a starting material an ethylenic compound having a
formyl group or an ethylenic compound which has at least two ethylenic
double bonds to which a formyl group is introduced, for example,
1,5-hexadiene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene,
cyclooctadiene, 7-octen-1-al or 2,7-octadien-1-ol.
As the rhodium compound usable in the present invention, a rhodium compound
which has catalytic activity for hydroformylation or which can be
converted to a compound with a catalytic activity for hydroformylation
under the hydroformylation reaction conditions can be employed. Examples
of such rhodium compound include Rh.sub.4 (CO).sub.12, Rh.sub.6
(CO).sub.16, Rh(acac)(CO).sub.2, rhodium oxide, rhodium chloride, rhodium
acetylacetonate and rhodium acetate. The rhodium compound is generally
used so that its concentration falls within a range of from 0.005
milligram atom to 5 milligram atom in terms of a rhodium atom per liter of
the hydroformylation reaction mixture.
A description will next be made of the tertiary organic phosphorus compound
represented by the formula (1) which is usable in the present invention.
Examples of the monovalent hydrocarbon group having 1-15 carbon atoms
represented by X.sub.1 or X.sub.2 in the above-described formula (1) of
the tertiary organic phosphorus compound include alkyl groups such as
n-butyl and octyl; aryl groups such as phenyl, tolyl and naphthyl;
cycloalkyl groups such as cyclohexyl and aralkyl groups such as benzyl.
Examples of the divalent hydrocarbon group having 1-15 carbon atoms
represented by X.sub.3 include 1,3-phenylene group and tetramethylene
group. Examples of the alkali metal represented by M include lithium,
sodium and potassium.
Specific examples of the tertiary organic phosphorus compound represented
by the formula (1) include sodium 3-diphenylphosphino-1-benzenesulfonate
(x.sub.1 =x.sub.2 =phenyl group, X.sub.3 =1,3-phenylene group, M=sodium),
lithium 3-diphenylphosphino-1-benzenesulfonate (X.sub.1 =X.sub.2 =phenyl
group, X.sub.3 =1,3-phenylene group, M=lithium), sodium
3-butylphenylphosphino-1-benzenesulfonate (X.sub.1 =n-butyl group, X.sub.2
=phenyl group, X.sub.3 =1,3-phenylene group, M=sodium), sodium
3-butylcyclohexylphosphino-1-benzenesulfonate (X.sub.1 =n-butyl group,
X.sub.2 =cyclohexyl group, X.sub.3 =1,3-phenylene group, M=sodium), sodium
3-bis(1-methylethyl)phosphino-1-benzenesulfonate (X.sub.1 =X.sub.2
=1-methylethyl group, X.sub.3 =1,3-phenylene group, M=sodium), lithium
3-dicyclohexylphosphino-1-benzenesulfonate (X.sub.1 =X.sub.2 =cyclohexyl
group, X.sub.3 =1,3-phenylene group, M=lithium), sodium
3-dicyclohexylphosphino-1-benzenesulfonate (X.sub.1 =X.sub.2 =cyclohexyl
group, X.sub.3 =1,3-phenylene group, M=sodium), potassium
3-dicyclohexylphosphino-1-benzenesulfonate (X.sub.1 =X.sub.2 =cyclohexyl
group, X.sub.3 =1,3-phenylene group, M=potassium), sodium
3-hexadecylphenylphosphino-1-benzenesulfonate (X.sub.1 =n-hexadecyl group,
X.sub.2 =phenyl group, X.sub.3 =1,3-phenylene group, M=sodium), sodium
3-dicyclohexylphosphino-1-propanesulfonate (X.sub.1 =X.sub.2 =cyclohexyl
group, X.sub.3 =trimethylene group, M=sodium), sodium
3-diphenylphosphino-1-propanesulfonate (X.sub.1 =X.sub.2 =phenyl group,
X.sub.3 =trimethylene group, M=sodium), sodium
4-diphenyl-phosphino-1-butanesulfonate (X.sub.1 =X.sub.2 =phenyl group,
X.sub.3 =tetramethylene group, M=sodium), sodium
4-(1,1-dimethylethyl)-(phenyl)phosphino-1-butanesulfonate (X.sub.1
=t-butyl group, X.sub.2 =phenyl group, X.sub.3 =tetramethylene group,
M=sodium), sodium 3-diethylphosphino-1-propanesulfonate (X.sub.1 =X.sub.2
=ethyl group, X.sub.3 =trimethylene group, M=sodium) and sodium
3-dihexylphosphino-1-propanesulfonate (X.sub.1 =X.sub.2 =n-hexyl group,
X.sub.3 =trimethylene group, M=sodium).
The tertiary organic phosphorus compounds represented by the formula (1) is
a water-soluble phosphine ligand.
The tertiary organic phosphorus compounds represented by the formula (1)
can be used singly or at least two of them can be used in combination.
The tertiary organic phosphorus compound represented by the formula (1) is
used in an amount within a range of at least 1 mmol, preferably at least 2
mmol, more preferably at least 5 mmol per liter of the hydroformylated
reaction mixture, from the viewpoints of the selectivity to the
hydroformylated product and thermal stability of the catalyst upon removal
of water from the rhodium-compound-containing water layer obtained by the
extraction described later. At the same time, it is desired to adjust its
amount to be at least 20 moles relative to 1 gram atom of rhodium.
Although no particular limitation is imposed on the upper limit of the
amount of the tertiary organic phosphorus compound represented by the
formula (1), it is desired to adjust its concentration to an extent not
causing precipitation of insoluble matters in the stage of removing water
from the catalyst-containing water layer. In consideration of the
manufacturing cost or the like, it is desired to control the concentration
of the tertiary organic phosphorous compound represented by the formula
(1) to be 200 mmol or smaller per liter of the hydroformylated reaction
mixture.
The polar organic compound used in the present invention is a compound
which is inert to the hydroformylation reaction of an olefinic compound
and also inert to the olefinic compound and its hydroformylated product;
which can be mixed homogeneously with the olefinic compound and the
reaction product, and separate into two layers, that is, a water layer and
an organic layer, when the reaction mixture containing said polar organic
compound is mixed with water; and at least one portion of which can be
extracted in the water layer from the reaction mixture. The polar organic
compound can preferably be mixed homogeneously with the tertiary organic
phosphorus compound represented by the formula (1).
Examples of such a polar organic compound include sulfoxides such as
dimethyl sulfoxide, sulfones such as sulfolane, carbonates such as
ethylene carbonate, amides such as N-methylpyrrolidone and
N,N-dimethylformamide, nitrites such as acetonitrile, diols such as
ethylene glycol and butanediol, polyalkylene glycols such as diethylene
glycol or polyethylene glycol (number-average molecular weight: 400),
polyalkylene glycol monomethyl ethers such as polyethylene glycol
monomethyl ether (number average molecular weight: 400), and polyalkylene
glycol dimethyl ethers such as triethylene glycol dimethyl ether,
tetraethylene glycol dimethyl ether and polyethylene glycol dimethyl ether
(number average molecular weight: 400). Among them, dimethyl sulfoxide,
N-methylpyrrolidone, N,N-dimethylformamide, polyethylene glycol having a
number average molecular weight of not smaller than 300 but not larger
than 600 and polyethylene glycol dimethyl ether having a number average
molecular weight of not smaller than 300 but not larger than 600 are
preferred from the viewpoints of its extraction recovery ratio into the
water layer and separability from water after extraction. In addition,
they are comparatively easily available so that they are preferable polar
organic compounds for the industrial practice of the process of the
present invention.
These polar organic compounds can be used singly or at least two of these
compounds can be used as a mixture.
The polar organic compound is generally used so that its concentration in
the hydroformylated reaction mixture falls within a range of not lower
than 2 vol. % but not higher than 30 vol. %, preferably within a range of
not lower than 5 vol. % but not higher than 20 vol. %.
The hydroformylation reaction is generally conducted at the temperature
within a range of 40.degree.-140.degree. C., preferably
70.degree.-120.degree. C. The molar ratio of hydrogen to carbon monoxide
used for the reaction generally falls within a range of from 1:2 to 5:1 as
an inlet gaseous ratio. The reaction pressure generally falls within a
range of from normal pressure to 300 atmospheric pressure, preferably
within a range of 2-100 atomospheric pressure.
The hydroformylation reaction can be effected in a continuous manner or
batch-wise manner in a known reaction apparatus such as stirring-type
reaction vessel or bubble-column type reaction vessel.
The reaction mixture obtained by the above-described hydroformylation
reaction is subjected to extraction with water, so that a catalyst
component composed of the rhodium compound and the tertiary organic
phosphorus compound represented by the formula (1), and the polar organic
compound may be separated. It is preferred that the volume ratio of water
relative to the reaction mixture falls within a range of not lower than
1/20 but not higher than 2/1, preferably within a range of not lower than
1/20 but not higher than 1/1.
The extraction temperature generally falls within a range of
10.degree.-90.degree. C. The extraction is generally carried out in an
atmosphere of an inert gas such as nitrogen, helium or argon or a gaseous
mixture of hydrogen and carbon monoxide.
The separability of the organic layer from the water layer in the above
extraction depends on the polarities of the olefinic compound (starting
material) and the resulting aldehyde, extraction temperature, the content
of the polar organic compound in the reaction mixture or the like. In
general, the higher the extraction temperature becomes or the higher the
concentration of the polar organic compound becomes, the separability
tends to be improved.
By such an extraction, the olefinic compound (starting material) and
hydroformylated product are separated into the organic layer (the
remaining layer after extraction), while the rhodium compound and the
tertiary organic phosphorus compound represented by the formula (1) (which
may hereinafter be called "catalytic component" collectively) and the
polar organic compound are transferred to the water layer (extract layer).
The organic layer contains small amounts of the catalytic component and
polar organic compound in addition to the starting material and
hydroformylated product. Accordingly, it is advantageous, from the
viewpoint of industrially carrying out the process of the present
invention, to subject again the resulting organic layer to extraction with
water in order to make the recovery ratio of the catalytic component and
the polar organic compound higher. In this case, no upper limit is imposed
on the amount of water, but water is generally used at a volume ratio of
not higher than an equivalent volume relative to that of the organic
layer.
Even if the recovery ratio of the catalytic component and the polar organic
compound is thus optimized, their loss sometimes reaches the level which
cannot be neglected. In such a case, the catalytic component and polar
organic compound may be added newly as needed.
The water layer containing the catalytic component and polar organic
compound obtained by the above extraction is concentrated by the removal
of water. For the removal of water, a known method can be applied without
particular limitation. Among the known method, evaporation under reduced
pressure is convenient. In this case, in order to avoid the deactivation
of the catalyst such as thermal deterioration, it is desired to remove
water at a temperature as low as possible. The temperature generally falls
within a range of from 30.degree. C. to 100.degree. C. The pressure at the
evaporation is generally within a range of from 300 mmHg to 10 mmHg.
It is necessary to remove water until the separation of the reaction
mixture into an organic layer and a water layer is not observed when the
resulting concentrate obtained is recycled to the hydroformylation
reaction of an olefinic compound.
In the present invention, the separation of the reaction mixture into an
organic layer and a water layer can be avoided by decreasing the content
of water in the concentrate when the concentrate is recycled to the
hydroformylation reaction of an olefinic compound. It is, however,
preferred not to carry out the removal of water excessively, because an
extreme reduction in the water content in the concentrate requires a great
amount of heat, which increases a manufacturing cost and also increases an
amount of heat applied to the catalyst to cause thermal deterioration of
the catalyst.
The water layer containing the catalytic component and the polar organic
compound obtained by the above-described extraction, and the concentrate
obtained by removing water from the water layer are generally a little
alkaline. In the present invention, at least one acidic substance selected
from sulfonic acids is added to the water layer or the concentrate to
adjust it to the neutral side.
Specific examples of the acidic substance selected from sulfonic acids
include benzenesulfonic acid, toluene-sulfonic acid and
3-diphenylphosphino-1-benzenesulfonic acid. Among them, a
phosphorus-containing sulfonic acid represented by the following formula
(2):
P(X.sub.4) (X.sub.5) (X.sub.6 --SO.sub.3 H) (2)
wherein X.sub.4 and X.sub.5 each independently represents a monovalent
hydrocarbon group having 1-15 carbon atoms and X.sub.6 represents a
divalent hydrocarbon group having 1-15 carbon atoms, such as
3-diphenylphosphino-1-benzenesulfonic acid, is preferred.
Examples of the monovalent hydrocarbon group having 1-15 carbon atoms
represented by X.sub.4 or X.sub.5 include alkyl groups such as n-butyl and
octyl; aryl groups such as phenyl, tolyl and naphthyl; cycloalkyl groups
such as cyclohexyl and aralkyl groups such as benzyl. Examples of the
divalent hydrocarbon group having 1-15 carbon atoms represented by X.sub.6
include 1,3-phenylene group and tetramethylene group.
Specific examples of the phosphorus-containing sulfonic acid represented by
the formula (2) include 3-diphenylphospino-1-benzenesulfonic acid (X.sub.4
=X.sub.5 =phenyl group, X.sub.6 =1,3-phenylene group),
3-butylphenylphosphino-1-benzenesulfonic acid (X.sub.4 =n-butyl group,
X.sub.5 =phenyl group, X.sub.6 =1,3-phenylene group),
3-butylcyclohexylphosphino-1-benzenesulfonic acid (X.sub.4 =n-butyl group,
X.sub.5 =cyclohexyl group, X.sub.6 =1,3-phenylene group),
3-bis(1-methylethyl)phosphino-1-benzenesulfonic acid (X.sub.4 =X.sub.5
=1-methylethyl group, X.sub.6 =1,3-phenylene group),
3-dicyclohexylphosphino-1-benzenesulfonic acid (X.sub.4 =X.sub.5
=cyclohexyl group, X.sub.6 =1,3-phenylene group),
3-hexadecylphenylphosphino-1-benzenesulfonic acid (X.sub.4 =n-hexadecyl
group, X.sub.5 =phenyl group, X.sub.6 =1,3-phenylene group),
3-dicyclohexylphosphino-1-propanesulfonic acid (X.sub.4 =X.sub.5
=cyclohexyl group, X.sub.6 =trimethylene group),
3-diphenylphosphino-1-propanesulfonic acid (X.sub.1 =X.sub.5 =phenyl
group, X.sub.6 =trimethylene group), 4-diphenylphosphino-1-butanesulfonic
acid (X.sub.4 =X.sub.5 =phenyl group, X.sub.5 =tetramethylene group),
4-(1,1-dimethylethyl)(phenyl)phosphino-1-butanesulfonic acid (X.sub.4
=t-butyl group, X.sub.6 =phenyl group, X.sub.6 =tetramethylene group),
3-diethylphosphino-1-propanesulfonic acid (X.sub.4 =X.sub.5 =ethyl group,
X.sub.6 =trimethylene group) and 3-dihexylphosphino-1-propanesulfonic acid
(X.sub.4 =X.sub.5 =n-hexyl group, X.sub.5 =trimethylene group).
Such an acidic substance can be added as it is or as a solution dissolved
in water or a polar organic compound.
By the addition of an acidic substance, the amount of a basic substance in
the water layer or concentrate decreases.
The amount of the acidic substance is determined depending on the amount of
a basic substance. Described specifically, it is determined after the
amount of the basic substance in the above water layer or concentrate is
measured by a pH-meter or in a known method such as titration. Since the
amount of the basic substance differs with the kind and amount of the
olefinic compound which is a starting material, conditions of
hydroformylation reaction, the kind of rhodium compound, the kinds and
amounts of the tertiary organic phosphorus compound represented by the
formula (1) and the polar organic compound or extraction conditions with
water, the amount of the acidic substance cannot be specified in a
wholesale manner. It is, however, preferred to add the acidic substance in
an amount so that the water layer or concentrate can be adjusted to almost
neutral.
The acidic substance can be added in an amount exceeding the amount
necessary for the neutralization of the basic substance. But the addition
of too excess amount of the acidic substance causes not only corrosion of
the reaction apparatus but also reduction in the reaction rate. Therefore,
it is not preferred to add the acidic substance excessively. The upper
limit of the amount of the acidic substance is set so that the acidic
substance may exist preferably in the concentrate in an amount of about 3
mmol per liter of the concentrate, more preferably in an amount of about 1
mmol per liter of the concentrate.
The acidic substance is generally added after water is removed from the
water layer, but it is also possible to add the acidic substance prior to
the water removal. In this case, water is removed after the addition of
the acidic substance.
The acidic substance can be added either continuously or discontinuously at
appropriate intervals.
Incidentally, treatment with a strong-acid-type ion exchange resin such as
a sulfonic acid type resin, instead of the addition of the acidic
substance, can reduce the amount of the basic substance in the water layer
or the concentrate and achieve the similar effects as above.
It is advantageous, from the viewpoint of industrially carrying out the
process of the present invention, to, after the addition of acidic
substance as above, recycle the concentrate, which contains the rhodium
compound, the tertiary organic phosphorus compound represented by the
formula (1) and the polar organic compound, to the hydroformylation
reaction of an olefinic compound while maintaining its temperature within
a range of 30.degree.-80.degree. C. to avoid the thermal deterioration of
the rhodium compound.
From the organic layer after the extraction of the catalytic component, an
aldehyde can be obtained as a product in a known method such as
distillation or crystallization. Alternatively, the organic layer
containing the aldehyde can be used, as it is, as a starting material for
the reaction such as oxidation or hydrogenation.
Any one of the above-described operations such as hydroformylation
reaction, separation of the catalytic component by the extraction with
water, removal of water from the water layer and the addition of an acidic
substance can be carried out in a batch-wise manner or continuous manner.
The present invention will hereinafter be described more specifically by
examples. It should, however, be borne in mind that the present invention
will not be limited to or by the following examples.
EXAMPLE 1
The hydroformylation reaction of 7-octen-1-al was carried out in a
continuous manner by using the reaction apparatus, extraction apparatus
and a thin-film evaporation apparatus described subsequently.
Reaction apparatus
A stainless-made autoclave which is equipped a starting material feed pump,
a catalyst liquid feed pump, a supplemental catalyst liquid feed pump, a
pressure regulator for feeding of a gaseous mixture of carbon monoxide and
hydrogen, a reaction mixture feed pump, a temperature controller, an
electromagnetic stirrer with four baffles and an off-gas purge port.
The starting material, 7-octen-1-al, is fed into the autoclave through the
starting material feed pump, while the gaseous mixture of carbon monoxide
and hydrogen is introduced into the autoclave through the pressure
regulator for feeding of the gaseous mixture of carbon monoxide and
hydrogen and is then discharged from the reaction system through the
off-gas purge port.
The concentrate containing a catalytic component and a polar organic
compound which is obtained by the extraction and concentration is fed
through the catalyst liquid feed pump, and the supplemental portions of
the catalytic component and polar organic compound are fed through the
supplemental catalyst liquid feed pump, respectively to the autoclave. The
reaction mixture is then fed to the extraction apparatus through the
reaction mixture feed pump.
Extraction apparatus
A mixer settler type extractor equipped with a water feed pump, a
temperature controller, an organic layer feed pump, a water layer feed
pump, an stirrer and a peeping glass.
The organic layer (the remaining layer after extraction) is fed through the
organic layer feed pump to a storage tank having an internal volume of 20
liters. The water layer (extract layer) is fed through the water layer
pump to the thin-film evaporation apparatus.
Thin-film evaporation apparatus
A thin-film evaporation apparatus equipped with a vacuum pump, a pressure
controller, a cooler, a temperature controller and a concentrate receiver.
The concentrate obtained is fed from the concentrate receiver to the
reaction apparatus (autoclave) through the catalyst liquid feed pump.
The olefinic compound, rhodium compound, tertiary organic phosphorus
compound represented by the formula (1) and polar organic compound
employed are as follows:
Olefinic compound: 7-octen-1-al (containing 10 vol. % of 1-octanal)
Rhodium compound: rhodium dicarbonyl acetylacetonate ›Rh(acac) (CO).sub.2 !
Tertiary organic phosphorus compound represented by the formula (1):
Sodium 3-diphenylphosphino-1-benzenesulfonate which will hereinafter be
abbreviated as "TPPS-Na")
Polar organic compound: polyethylene glycol dimethyl ether having a number
average molecular weight of 400.
The operation conditions in a stationary state are as follows:
1. Hydroformylation reaction
Reaction temperature: 80.degree. C.
Reaction pressure: 30 kg/cm.sup.2 G (gauge pressure) (partial pressure
ratio of carbon monoxide to hydrogen=1:1)
Off-gas rate: 20 liters/h
Volume of liquid to be reacted: 380 ml
Feeding rate of starting materials: 20 ml/h
Here, the feeding rates of the catalytic component and polar organic
compound, as a sum of those recovered by extraction and supplemented, are
as follows:
Rhodium compound: 0.0022 mmol/h (of it, that supplemented: 0.0004 mmol/h)
Tertiary organic phosphorus compound represented by the formula (1): 0.11
mmol/h (of it, that supplemented: 0.03 mmol/h)
Polar organic compound: 2 ml/h (of it, that supplemented: 0.4 ml/h)
2. Extraction of the catalyst
Temperature inside the mixer settler: 50.degree. C.
Feeding rate of water: 7 ml/h
Volume of liquid in the mixer settler: 300 ml
3. Water evaporation by a thin-film evaporator
Temperature: 90.degree. C.
Pressure: 70 mnHg
Volume of concentrate: 50 ml
Here, the water content in the concentrate obtained by water evaporation
was maintained at 10 wt. % or lower. The concentrate was fed to the
hydroformylation reaction at a rate of about 1.7 ml/h.
An analysis of the organic layer (the remaining layer after extraction) in
a stationary state with gas chromatography shows that the conversion of
7-octen-1-al was 95% and the reaction products were 1,9-nonanedial,
2-methyl-1,8-octanedial and a higher-boiling point condensed material. The
ratio of 1,9-nonanedial to 2-methyl-1,8-octanedial was 75:25.
At the time when 384 hours had passed in a stationary state, the
concentrate obtained by water evaporation was sampled, followed by
titration to determine the amount of the acidic substance necessary for
the neutralization of the basic substance in the concentrate. As a result,
it has been found that the amount of the acidic substance was 4 milligram
equivalents per liter of the concentrate. Here, 50 mg of
3-diphenylphosphino-1-benzenesulfonic acid (which will hereinafter be
abbreviated as "TPPS") were added to the concentrate and the
hydrofolmylation reaction was continued. 20 mg of TPPS were thereafter
added to the concentrate at the intervals of 24 hours.
The time for the reaction and the amount of the higher-boiling point
condensed material in the organic layer (remaining layer after extraction)
at that time are shown in Table 1.
TABLE 1
______________________________________
Amount of a higher-boiling
Time for the operation in
point condensed material in the
a stationary state (hr)
organic layer (wt. %)
______________________________________
24 1
120 5
240 11
360 16
480 4
______________________________________
EXAMPLE 2
In Example 1, at the time when 240 hours had passed in a stationary state,
the concentrate obtained by water evaporation was sampled, followed by
titration to determine the amount of the TPPS necessary for the
neutralization of the basic substance in the concentrate. As a result, it
has been found that the amount of TPPS was 1.2 g per liter of the
concentrate.
In an electromagnetic stirring type autoclave having an internal volume of
100 ml, a predetermined amount of TPPS, 5 ml of the concentrate which had
been obtained by the evaporation of water at the time when 240 hours had
passed in a stationary state in Example 1 and 20 ml of 7-octen-1-al
(purity 90%, 0.12 mol, containing 10% of 1-octanal) were charged while
avoiding their contact with air. The pressure in the autoclave was
maintained at 30 kg/cm.sup.2 G (gauge pressure) with a gaseous mixture of
hydrogen and carbon monoxide at a ratio of 1:1 (molar ratio). An off-gas
was discharged at a rate of 10 liters/h and internal temperature was
raised to 70.degree. C. while stirring. The reaction was conducted for 4
hours under that condition. The internal temperature was then raised to
100.degree. C. over one hour and the reaction was conducted for 5 hours
under that condition. The reaction mixture obtained was analyzed by gas
chromatography to determine the conversion of 7-octen-1-al and amount of
higher-boiling point condensed material. Results are shown in Table 2.
TABLE 2
______________________________________
Amount of higher-
boiling point
Conversion of 7-
condensed material
Amount of octen-1-al ›wt. % (Note), after
TPPS added (after 4 hours,
completion of the
(mg) mol %) reaction!
______________________________________
0 36 21
6 41 2
9 26 2
______________________________________
(Note) The amount of a higher-boiling point condensed material in the
hydroformylated reaction mixture
EXAMPLE 3
In electromagnetic stirring type autoclave equipped with a gas inlet and a
sampling port and having an internal volume of 300 ml, 1.29 mg (0.005
mmol) of rhodium dicarbonyl acetylacetonate, 800 mg (2 mmol) of TPPS-Na,
10 ml of dimethyl sulfoxide and 90 ml of 7-octen-1-al (purity: 90%, 0.55
mol, containing 10% of 1-octanal) were charged avoiding their contact with
air. The pressure inside of the autoclave was maintained at 30 kg/cm.sup.2
G (gauge pressure) with gaseous mixture of hydrogen and carbon monoxide at
a ratio of 1:1 (molar ratio). An off-gas was discharged at a rate of 10
liters/h and the internal temperature was raised to 90.degree. C. while
stirring. The reaction was carried out for 4 hours under those conditions.
The reaction mixture was then fed into a three-necked flask, filled
sufficiently with a gaseous mixture of hydrogen and carbon monoxide at a
ratio of 1:1 (molar ratio) in advance and having an internal volume of 250
ml, avoiding its contact with air. While 20 ml of water were added and the
internal temperature was maintained at 25.degree. C., the reaction mixture
was stirred for 10 minutes under the atmosphere of the gaseous mixture of
the above composition. After the stirring was stopped, the reaction
mixture was transferred to the separation tank filled with a gaseous
mixture of hydrogen and carbon monoxide and then allowed to stand, which
separated the reaction mixture into an organic layer (upper layer) and a
water layer (lower layer). The water layer was transferred to a flask
filled with nitrogen and having an internal volume of 200 ml, which was
immersed in a water bath kept at 60.degree. C. Water was distilled by the
gradual reduction of the pressure to 15 mmHg. When the distillation of
water was completed, the pressure was adjusted to normal one with a
nitrogen while maintaining the temperature at 60.degree. C.
To the concentrate obtained, 80 mg of TPPS-Na, 1.5 ml of dimethyl sulfoxide
and 90 ml of 7-octen-1-al were added, followed by mixing under stirring.
Then, the concentrate mixture was transferred again to the autoclave
avoiding its contact with air, and hydroformylation reaction was carried
out for four hours under the reaction conditions similar to those employed
for the first reaction. The extraction, water evaporation, and addition of
TPPS-Na, dimethyl sulfoxide and starting materials were also conducted
under similar conditions with those employed for the first reaction.
In this manner, hydroformylation reaction was repeated and hydroformylation
reaction of 7-octen-1-al was carried out 22 times in total. Here,
concerning the organic layer (remaining layer after extraction) obtained
by the separation of the water layer containing the catalytic component
and the polar organic compound, analysis of the product was carried out
with gas chromatography.
Incidentally, to the concentrate of the water layer obtained by the
treatment of the 10-th reaction mixture, 0.31 mg of rhodium dicarbonyl
acetylacetonate was added. In addition, the concentrate of the water layer
obtained by the treatment of the 20-th reaction mixture was subjected to
titration. As a result, it has been found that the amount of TPPS
necessary for the neutralization of the concentrate was 2 g per liter of
the concentrate. To the concentrate, 0.31 mg of rhodium dicarbonyl
acetylacetonate and 20 mg of TPPS were added. Reaction times and amounts
of 1,9-nonanedial, 2-methyl-1,8-octanedial and higher-boiling point
condensed material are shown in Table 3.
TABLE 3
______________________________________
Amount (g)
Higher-
boiling point
Reaction 1,9- 2-Methyl-1,8-
condensed
times Nonanedial octanedial material
______________________________________
1 46 15 0
5 44 15 1
10 41 13 3
15 43 14 4
20 39 13 7
21 45 15 1
22 46 15 1
______________________________________
As is evident from Tables 1-3, it has been found that the amount of the
higher-boiling point condensed material was suppressed by the addition of
TPPS to the concentrate of the water layer obtained by the extraction of
the hydroformylation reaction mixture with water.
EXAMPLE 4
In an electromagnetic stirring type autoclave equipped with a gas inlet and
a sampling port and having an internal volume of 300 ml, 2.58 mg (0.01
mmol) of rhodium dicarbonyl acetylacetonate, 2.0 g (5 mmol) of TPPS-Na, 50
ml of N-methylpyrrolidone and 45 ml (0.287 mol) of 1-octene were charged
avoiding their contact with air . The pressure inside of the autoclave was
maintained at 30 kg/cm.sup.2 G (gauge pressure) with a gaseous mixture of
hydrogen and carbon monoxide at a ratio of 1:1 (molar ratio). The internal
temperature was raised to 90.degree. C. under stirring, under which
condition the reaction was effected for 3 hours. The internal temperature
was raised further to 110.degree. C., under which condition the reaction
was conducted for 4 hours.
The reaction mixture was then fed into a three-necked flask, filled
sufficiently with a gaseous mixture of hydrogen and carbon monoxide at a
ratio of 1:1 (molar ratio) in advance and having an internal volume of 250
ml, avoiding its contact with air. While 20 ml of water were added and the
internal temperature was maintained at 25.degree. C., the reaction mixture
was stirred for 10 minutes under the atmosphere of the gaseous mixture of
the above composition. After stirring was stopped, the reaction mixture
was transferred to the separation tank filled with a gaseous mixture of
hydrogen and carbon monoxide and then allowed to stand, which separated
the reaction mixture into two layers, that is, an organic layer (upper
layer) and a water layer (lower layer). The water layer was transferred to
a flask filled with nitrogen and having an internal volume of 200 ml,
followed by immersion in a water bath kept at 60.degree. C. Water was
distilled by the gradual reduction of the pressure to 15 mmHg. When the
distillation of water was completed, the pressure was adjusted to the
normal one with a nitrogen while maintaining the temperature at 60.degree.
C.
To the concentrate obtained, 100 mg of TPPS-Na, 8.6 ml of
N-methylpyrrolidone and 45 ml of 1-octene were added, followed by mixing
under stirring. Then, the concentrate mixture was transferred again to the
autoclave avoiding its contact with air, and hydroformylation reaction was
carried out under the reaction conditions similar to those employed for
the first reaction. The extraction, water evaporation, and addition of
TPPS-Na, N-methylpyrrolidone and 1-octene were also conducted under
similar conditions with those employed for the first reaction.
In this manner, hydroformylation reaction was repeated and hydroformylation
reaction was carried out 17 times in total. Here, the organic layer
obtained by the separation of the water layer containing the catalytic
component and N-methylpyrrolidone was subjected to analysis of the product
with gas chromatography. In addition, the amount of higher-boiling point
condensed material in the organic layer was determined by the gas
chromatographic analysis of the concentrate obtained from said organic
layer by the gradual reduction of the pressure to 5 mmHg at 110.degree.
C., which is about 15-fold to 20-fold concentration relative to the
original organic layer.
Incidentally, to each of the concentrate of the water layer obtained by the
treatment of the 5-th, 10-th and 15-the reaction mixtures, respectively,
1.29 mg of rhodium dicarbonyl acetylacetonate was added. Analysis of the
water layer obtained by the treatment of the 15-th reaction mixture with a
pH-meter shows that the addition of 0.3 g of TPPS per liter of the
concentrate changes the property of the concentrate from basic to acidic.
To the concentrate, 12 mg of TPPS was added.
Reaction times and results of analysis of the organic layer obtained by the
treatment of the reaction mixture are shown in Table 4.
TABLE 4
______________________________________
Amount (wt. %)
Aldehyde having 9
Higher-boiling point
Reaction times
carbon atoms (Note)
condensed material
______________________________________
1 82 1.2
11 79 2.2
15 74 3.0
16 78 1.4
17 79 1.5
______________________________________
(Note) Mixture of 1-nonanal and 2-methyloctanal
As evident from Table 4, it has been found that the amount of the
higher-boiling point condensed material can be suppressed by the addition
of TPPS to the concentrate of the water layer obtained by the extraction
of the hydroformylation reaction mixture with water.
INDUSTRIAL UTILIZATION
The hydroformylation process of the present invention is useful as an
industrial preparation process of various aldehydes useful as a starting
material for fine chemicals such as pharmaceuticals and agricultural
chemicals, alcohols for a plasticizer or starting materials such as diol,
dicarboxylic acid, and diamine for the synthesis of a polymer compound.
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